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Commercial electric vehicles nowadays are powered by a battery system containing one kind of lithium-ion battery cell. Due to the fixed ratio of the cells’ maximum power to nominal energy, the possibilities for designing power and energy of the battery pack independently are limited. The battery system’s energy and maximum power can only be scaled by adapting the number of cells and modules, and the parameters furthermore depend on the characteristics of the cells used. Additional power electronics in the form of one or more dc/dc converters can be used to form a hybrid battery system comprised of more than one pack and different cell technologies. This allows for individually designing each battery pack and thus optimizing the overall battery system specification. This work presents a battery dimensioning and optimization approach for single pack and hybrid battery systems. It is based on an evolutionary optimization algorithm and a detailed, modular Matlab-Simulink vehicle model. Studies on the advantages of hybrid batteries for different vehicle classes were carried out. Results indicate that optimized hybrid battery systems can lead to weight and volume savings and further advantages in total cost of ownership, for example, by enhanced battery life time or reduced investment costs. On the other hand, they require more complex control logic, which is also discussed in this paper.